Phase diagram and spin-glass phenomena in electron-doped La1−xHfxMnO3 (0.05 ≤ x ≤ 0.3) manganite oxides

Abstract

The effects of tetravalent hafnium doping on the structural, transport, and magnetic properties of polycrystalline La1−xHfxMnO3 (LHMO) (0.05 ≤ x ≤ 0.3) were investigated systematically. LHMO exhibited a typical colossal magnetoresistance effect via the double-exchange between Mn2+ and Mn3+ ions, instead of that between Mn3+ and Mn4+ ions in hole-doped manganites. A phase diagram was obtained for the first time through magnetization and resistance measurements in a broad temperature range. As the Hf concentration varied from x = 0.05 to 0.3, the Curie point and metal-to-insulator transition temperature increased significantly, whereas the magnetization and resistivity decreased remarkably. An abnormal enhancement of the magnetization was observed at about 42 K. It was further confirmed that a second magnetic phase MnO2 in LHMO gives rise to such a phenomenon. The possible causes are discussed in detail. The dynamic magnetic properties of LHMO, including relaxation and aging processes, were studied, demonstrating a spin-glass state at low temperature accompanied by a ferromagnetic phase.